Biologically toxic compositions containing boron-phenol complexes and methods



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BIOLOGICALLY TOXIC COMPOSITIONS CONTAIN- IN( BORON-PHENOL COMPLEXES ANDMETH- OD David R. Stern, Fullerton, and Friedrich I. Weck, HaciendaHeights, Caiif., assignors to American Potash & Chemical Corporation,Los Angeles, Calif., a corporation of Delaware No Drawing. Filed Jan.14, 1965, Ser. No. 425,609

12 Claims. (Cl. 16730) This is a continuation-in-part of applicationSerial Number 187,943, filed April 16, 1962, now abandoned.

This invention relates, in general, to biologically toxic compositionsand to methods of combating biological growth. More specifically, thebiologically toxic compositions comprise a major amount of inert matterand an effective amount of certain toxic ontho-substituted-phenolcomplexes.

Considerable difiiculty has been experienced in trying to obtain broadprotection against undesirable biological growth through the use of asingle biological toxicant The use of a single toxicant capable ofinhibiting undesirable biological growth is highly desirable because itre duces the number of toxic ingredients required in biologically toxiccompositions.

Further, previous biological toxicants have been limited in the scope oftheir usefulness because they were compatible or could be renderedcompatible with only a limited number of substratum.

The term substratum as used in this specification and in the appendedclaims means any substance which it is desired to protect from undesiredbiological growth and which is capable of retaining on its surface orwithin itself, or both, a toxic amount of the biological toxicants whichare more specifically described hereafter. The term includes liquids,powders, granular material, unitary solids, emulsions, solutions,dispersions, and heterogeneous systems such as a liquid-liquid,liquid-solid, or solidsolid type.

Broadly, the biologically toxic compositions according to this inventionare comprised of a major proportion of (A) a substratum and (B) a toxicamount of an orthosubstituted-phenol complex. Theortho-substituted-phenol complex portion of these compositions comprisesphenols having the formulas:

R1 I'M R -o oa M \B/ on on I 0 R2 R2 (1) CH /B\ M 0 OH R2 (11) Thesephenol complexes may be used singly or in combinations of two or more.

In the above formulae, R can be any of the substituents, chlorine,fluorine, bromine, iodine, alkyl, cycloalkyl or aryl; R can be any ofchlorine, fluorine, bromine, iodine, alkyl, cycloalkyl or aryl, with theprovision that only one of R and R can be halogen on any given com-3,266,981 August 16, 1966 pound; R can be any of hydrogen, alkyl,cycloalkyl or aryl substituents; M can be any of the alkali metals,lithium, sodium, potassium, rubidium, or cesium; or ammonium. When oneof R or R is a halogen, the other can be an alkyl or cycloalkyl groupcontaining from 4 to 24 carbon atoms or an aryl group containing from 6to 24 carbon atoms. When neither R nor R is a halogen, either one can bean alkyl group having from 2 to 22 carbon atoms, a cycloalkylsubstituent having from 4 to 22 carbon atoms or an aryl group havingfrom 6 to 22 carbon atoms, provided that there is a total of between 8and 24 carbon atoms present in the two substituents combined. When R isnot hydrogen, it can be either an alkyl group containing from 1 to 7carbon atoms, a cycloalkyl group containing from 4 to 7 carbon atoms oran aryl group containing from 6 to 10 carbon atoms. Thus, the totalnumber of carbon atoms in the R and R substituents combined is at least4 when one of these substituents is halogen and at least 8 when neitherR nor R is halogen.

The method of inhibiting or substantially minimizing the growth ofbiological material on a substratum, comprises providing such substratumwith an amount of'the above described toxicants sufficient to render theresultant substratum-toxicant composite, toxic to biological material.,

When the substratum is a finely divided solid or powder such as talc,clay, bentonite, or the like, the toxicant may be associated with it by,for example, mixing, blending, shaking, or by like means.

When the substratum is a liquid or an emulsion, the,

toxicant can be associated with it by dispersing, dissolving, orsuspending the compound in the liquid or emulsion.

When the substratum is a unitary solid such as wood, fabric, fur,leather, organic plastic materials, or the like, the toxicant can beassociated with it in many ways such as, for example, by dusting orspraying the toxicant onto the surface of the solid either with orwithout a solvent or diluent; or by soaking the unitary solid in a largebody of liquid containing dissolved toxicant for a period of [timesutficient to impregnate the solid with the desired concentration oftoxicant; and the like. Pressure impregnation techniques also can beused, employing a pressure chamber in which the toxicant is introducedat elevated temperatures, either as a vapor or as a liquid entrained inanother vapor such as toxicant-in-steam, and the like.

Hardenable coatings such as paints, enamels, varnishes, and like surfacecoatings can be associated with the toxicant by dispersing, grindinginto, polymerizing or dissolving the toxic compounds in the fluidcoating before the latter has hardened or by spraying or dusting thetoxic compounds on the coating after it has been applied to a surface.

The substituents R, R and R of the ortho-substitutedphenol complexportion (B) of the composition, preferably are chosen so that theresulting toxicant is compatible with the desired substratum portioii(A). Thus, if the substratum is water, R should be a low molecularweight substituent such as methyl, R should be halogen or a lowmolecular weight alkyl and R should be either hydrogen or a lowmolecular weight substituent such as methyl. If the substratum is aliquid hydrocarbon, R should be a large substituent such as octyl ornonyl, while the selection of R and R is not critical.

This invention is particularly useful in preventing the growth ofundesirable biological matter in liquid hydrocarbons. There is .atendency for an aqueous phase to form in contact with a liquidhydrocarbon, due to absorption and condensation of atmospheric moisture.For this reason, during storage, liquid hydrocarbons are almost alwaysin contact with an aqueous phase. Certain micro-organisms live in thisaqueous phase and feed on the hydrocarbon. Thus, the interface betweenthe aque- 011s and hydrocarbon phases is often covered with a growth ofmicro-organisms. An eifective amount of toxicant dissolved in thehydrocarbon phase substantially inhibits the growth of thesemicro-organisms.

The term normally liquid hydrocarbon as used in the instantspecification and in the appended claims includes gasoline, kerosene,naphtha, gas oil, cylinder stock, diesel fuel, jet fuel, heating oil,and the like. Normally, these hydrocarbons contain an average of fromabout four to fourteen carbon atoms, have a specific gravity or fromabout 0.6 to 0.95, an average molecular weight of from about 60 to 250,and an average boiling point of from about 40 F. to 700 F. Averageboiling point is defined as the temperature of the boiling mixture ofhydrocarbons when one half by weight of the hydrocarbons have beendistilled olf. In general, any hydrocarbon material from the lightestliquids through waxy solids to highly polymeric solids can be protectedfrom attack by biological material, according to this invention.

This invention is also useful in preventing the growth of undesirablebiological material on cellulosic substratum.

Cellulosic materials which can be provided with a toxic amount of theherein described toxicants, in accordance with this invention, includecellulosic films and filaments, fabrics, paper, Wood, variouscompositions including wood in one form or another, such as compositionsiCOlltaining wood fibres in a matrix of some other material and thelike. These cellulosic materials can be provided with a toxic amount ofthese compounds by any of the procedures described above, includingparticularly, impregnating as by soaking, treating the surface of thecellulosic materials, by spraying or dusting, and coating the surfacewith other compositions containing the toxic compounds such asvarnishes, lacquers, calcimine, oil and water base paints, papercoatings of various kinds, and the like.

' The preferred cellulosic material, according to this invention, iswood. Wooden articles provided with a toxic amount of the abovedescribed toxicants are extremely resistant to wood destroying fungusand insects. Many different types of wood can be protected in thismanner. Thus, pine, fir, hickory, mahogany, oak, ash, spruce, birch,aspen, maple and the like, can be protected from insects and microorganisms by providing them with a toxic amount of these compounds.

Wood can be provided with these compounds by any of the conventional,well-known procedures for impregnating woods with preservatives. Thesetoxicants, which are boron complexes, can be introduced into the wood ascomplexes or the complex can be tor-med in situ in the wood [by reactionbetween the corresponding ortho-alcoh'ol-phenol and boric acid or someother soluble boron compound. This reaction can be accomplished, forexample, by first impregnating the wood with one reactant, followed by asecond impregnation with the other reactant. Various other agents can beemployed with the toxicants, for example, surfactants which aid thepenenation of the toxicant into the wood can be used.

According to this invention, the toxicants can be in- :orporated in woodin an amount ranging from about ).1 percent by weight to about 0.05percent by weight. it will be understood that the concentration oftoxicant ormally will be greatest at the surface of the wood and villdecrease progressively with increasing depth into he wood.- For thisreason, the surface of the wood is iften provided with an excess oftoxicant so that the inerior will contain an effective amount of thecompound.

A further aspect of this invention comprises the proision of a toxicamount of the herein described toxicants with various substratum-surfacecoating compositions. The toxicants can be incorporated in a substratumsuch as paint to render the paint resistant to the growth of biologicalmaterials. These paints find particular utility when applied below thewater line on the hulls of seagoing vessels, where their anti-foulingproperties are particularly valuable.

The paints, according to this invention, which can be provided with atoxic amount of toxicant are comprised primarily of pigment and vehicle.

The volatile constituents in the paint vehicle include, for example,hydrocarbons such as aliphatic and mineral spirit cuts, aromatics suchas toluene and xylene, lacquer solvents, for example, esters such asbutyl acetate, and ketones such as methylethylketone, mixtures of two ormore vehicles, and the like. The non-volatile portions of the vehiclecan include, for example, natural drying oils such as linseed oil,synthetic resins such as glycerol phthalate or phenol-formaldehyde,lacquers which dry by solvent evaporation such as nitrocellulose andother thermoplastic resins, materials such as silicones, mixtures of twoor more non-volatile vehicles, and the like. The pigment portion of thepaint can be either inorganic or organic, including, for example, chalk,cadmium yellow, bone black, azurite, litharge, mica, ochre yellow,pumice, white lead, zinc white, talc, red lead, silica, and the like.These pigments may be used singly or in mixtures of two or more.

The gloss of the particular paint is conveniently regulated by adjustingthe proportion of pigment contained therein. In general, the lower theamount of pigment, provided it is present in a quantity suficient toprovide adequate covering, the glossier the paint.

According to this invention the toxicants can be incorporated in paintin an amount ranging from about 0.1 percent by weight to about 0.05percent by weight. When these toxicants are used in anti-fouling marinepaints to prevent the growth of various marine life on boat hulls, theyare provided in relatively large amounts, for example, in excess ofabout 4 percent.

The biological toxicants used in the present invention are stablecompounds which range from viscous liquids to crystalline 0r glassysolids. They are soluble in a wide range of solvents and as hereindescribed, can advantageously be tailored to fit the solubility problemsattendant the particular susbtratum involved. Theseortho-substituted-phenol complexes can be advantageously employed for avariety of commercial and industrial purposes, but they are particularlyuseful as biological toxicants. When used as biological toxicants, theyare effective at a concentration from as low as about one part permillion parts of substratum up to a concentration of about 1,000 partsper million parts of substratum.

The ortho-alcohol-phenols used in the preparation of the toxicants usedin this invention can be prepared conveniently by the reaction of aphenol having the formula:

with an aldhyde having the formula:

R CHO In the above formulas R, R and R have the values set forth above.This reaction is carried out in the presence of an alkaline catalyst. Ifan alkaline borate is used, the boron complex is produced. Treatment ofthe boron complex with acid will destroy the complex and produce thecorresponding ortho-alcohol-phenol. This preparation is described inmore detail in assignees copending application Ser. No. 118,526, filedJune 21, 1961.

Thus, when the reaction is carried out in the presence C r-C of analkaline borate, such as sodium borate, a novel boron complex formssubstantially as follows:

He r; 2 2RCHO NaBOz :2

The boron complex formed, as illustrated above, may be convenientlytreated with a quantity of a dilute mineral acid to break the complexand release the compound of this invention. In carrying out thesereactions, in addition to the sodium ion, the other alkali metals suchas lithium, potassium, rubidium, and cesium may be used as well as theammonium ion.

In the specification, claims and following specific examples, all partsand percentages are by weight unless otherwise indicated. The followingexamples are set forth to further illustrate and not to limit theinvention:

Example I This example illustrates the preparation of a toxicantadditive: 2-chloro-4-tertiarybutyl-6-methylolphenol.

A solution of 50 gm. of sodium hydroxide (1.25 mols) and 62 gm. of boricacid (1 mol) in 500 ml. of water is added to 181 gm. of raw2-chloro-4-tertiarybutylphenol (approximately 0.9 mol) and heated whilevigorously stirring. When a temperature of 65 C. is reached, theaddition of 100 ml. of a 36.1% aqueous solution of formaldehyde isbegun. The initially milky mixture clears after about minutes. Theaddition of formaldehyde is finished after two hours. After a thirdhour, the mixture turns cloudy and solidifies slowly while forming asoft crystalline mass. After standing overnight, the reaction mixture isrepulped in 5 liters of cold water for the removal of the water-solublecomponents, and 205 gm. of a white, flaky material is obtained by vacuumfiltration. After repulping in 600 ml. of benzene for the removal of theorganic impurities, 95 gm. of a white crsytalline material (boratecomplex) are obtained. The melting point is over 350 F. The crystals aretested for boron content by suspending one gram of the material in 30ml. of benzene and contacting the suspension three times with 60 ml. of0.1 N sulfuric acid, thus stripping the chelate of boron ions. The boroncontent of the aqueous phase is then determined by titration with alkaliin the presence of mannitol (Scotts Standard Methods of ChemicalAnalysis I, 5th edition, New York, D. Van Nostrand Publishing Co., 1939,p. 170). Boron equivalent to 30.5 ml. 0.1 N boric acid is found in theaqueous phase, and indicates that the precipitate consists of a mixtureof monoand di-saligenin borate complexes, as can be concluded from thefollowing calculations.

(a) The mono-saligenin borate complex:

One gm. of the above complex represents 0.0036 mol Na= C11H1504C1N3B M01wt. =280.498 Percent B, calculated=3.86

(b) The di-saligenin borate complex: C1 G1 I I CH3 Mol wt. =459.153

B CH3 Percent B, calcu1ated=2.35

CHsO OCH:

for which the boron content should be equivalent to 36 ml. of 0.1 Nboric acid.

One gm. of the di-saligenin complex corresponds to 0.0021 mol for whichthe boron content should be equivalent of 21 ml. of 0.1 N boric acid.

Since the titrated equivalent of the one gm. sample obtained bysynthesis represents a value between these calculatd figures, it can beconcluded that the precipitate consists of a mixture of monoanddi-saligenin borate complexes. The estimate-d conversion of phenol tosaligenin is 90%.

Example 11 A water-hydrocarbon system is prepared using diesel fuel andsea water. The fuel has an average of 12 carbon atoms, a specificgravity of 0.85, an average molecular weight of 170, and an averageboiling point of 500 F. The toxicant additive (the sodium salt of theboron complex of 2-chloro-4-nony1-6-methylolphenol) is dissolved in thehydrocarbon to produce a solution containing 0.005% of the toxicant inthe hydrocarbon. Water containing the fungus, Hormodendron, isintroduced into the hydrocarbon.

After constant agitation for a period of 7 days at a temperature of F.,under the same conditions, a substantially identical water-hydrocarbonsystem containing no toxicant shows-a substantial growth ofmicro-organisms while the solution containing the toxicant shows nodiscernible evidence of micro-organisms. The conditions of sea water andconstant agitation used in this example, closely approximate thosepresent in a ship at sea which contains fuel in storage.

Example 111 Two specimens of pine wood (Pinus radiata, such as are foundin Australia and New Zealand) measuring x 4" x 18 are treated asfollows:

The first specimen is impregnated by pressure injection with a saturatedaqueous solution of the sodium salt of the boron complex of2-butyl-4-butyl-6-( l-hydroxyethyl)-phenol. The second specimen isuntreated.

The two specimens are inoculated with the fungus Lensite trabea.

The inoculated ends of the two specimens are buried in loose sandy soilto a depth of six inches and allowed to stand undisturbed. The specimensare then carefully removed from the soil and cleaned. The untreatedspecimen shows extensive deterioration while the treated specimen issubstantially unchanged except for slight discoloration due to contactwith the soil.

Example IV A quantity of interior flat oil paint is prepared containing65% pigment, 14% non-volatile vehicle, which is primarily treateddryingoil, 21% turpentine solvent and 0.25% of the ammonium salt of theboron complex of 2-chlor0-4-nonyl-6-methylolphenol.

A second quantity of paint having substantially the same compositionexcept that it contains no 2-chloro- 4-nonyl-6-methy1olphenol complex,is prepared.

A line is drawn on a piece of 12 in. x 12 in. plywood so that it dividesthe surface into two halves, each measuring 6 in. x 12 in. One half ofthe plywood is given two coats of the complex-containing paint, whilethe other half is given two coats of the paint which contains nocomplex.

A culture medium is prepared containing the organism Aspergz'llus nigerin a medium having the composition:

Sucrose and agar 7 The culture medium is seeded with spores ofAspergillus niger and incubated for 46 hours at 25 to 27 C., and 80 to85% relative humidity, after which period of time the white mycelialstage of the mold is extended over the entire surface of the agar.

The painted plywood specimen is dipped in water and placed painted sidedown on the white mycelial growth so that half of the culture medium isin contact with the complex-containing paint and the other half of theculture medium is in contact with the paint which contains no complex.The whole specimen is further incubated while contact between the moldand painted surface is maintained.

The incubation is carried out at a temperature of 25 to 27 C., and 80%to 85% relative humidity for a period of 7 days. After this period oftime, the control sample of paint, which contains no complex, showssubstantial growth of dark sporulating mold growing on and in contactwith the painted surface. The complexcontaining paint showssubstantially no evidence of dark sporulating mold either on or incontact with the painted surface.

Suitable inert carriers for use in this invention include, for example,finely divided talc, oil-in-Water emulsions, mineral spirits, finelydivided bentonite, benzene, diatomaceous earth, carbontetrachloride,water and an inert wetting agent, acetone and the like.

Satisfactory results are also obtainable by substituting any one or moreof the following complexes in the above examples: the potassium salt ofthe boron complex of 2-chloro-4-(1,1,3,3-tetramethyl'butyl)6-methylolphenol, the sodium salt of the boron complex of2,4-di(tertiaryamyl)-6-methylolphenol, the lithium salt of the boroncomplex of 2-bromo-4-cumenyl-6-(1-hydr0xyethyl)- phenol, the ammoniumsalt of the boron complex of 2-iodo-4-benzyl-6-(1-hydroxy-2-phenylethyl)-phenol, the rubidium salt of theboron complex of 2-fluoro-4-isoamyl-6- methylolphenol, the cesium saltof the boron complex of 2-nonyl-4-iodo-6-(1-hydroxyethyl)-phenol, thesodium salt of the boron complex of2-methyl-4-pentadecyl-6-(l-hydroxy-2-cyclopentylethyl)-phenol, theammonium salt of the boron complex of2-cyclohexyl-4-cyclohexyl-6-methylolphenol, mixtures of two or more ofthese toxicants and the like. It will be understood that these boroncomplexes are generally present as a mixture of complexes having one andtwo substituted phenols per boron atom.

The organic substituents from which R, R and R can be selected can eachbe independently chosen from the following illustrative but not allinclusive list of organic substituents: alkyl substituents such asethyl, methyl, isoamyl, neopentyl, decyl, hexyl, propyl, Z-methylpentyl,S-methylhexyl, pentyl, dodecyl, butyl; cycloalkyl substituents such ascyclopentyl, cyclohexyl, cycloheptyl, pmethylcyclohexyl,3-ethylcyclopentyl, 3,5-dimethylcyclopentyl, cyclobutyl; arylsubstituents such as 2,4-xylyl, rn-cumenyl, phenyl, mesityl, biphenylyl,naphthyl, indanyl, tolyl and the like.

If R is an organic group, preferably it will be an alkyl group havingfrom 1 to 3 carbon atoms or a phenyl group. Organic substituents havingmore than these preferred limits of carbon atoms at this particularposition, tend to provide more steric hindrance than is desirable forthe formation of boron complexes or other reactions.

Preferred ortho-substituted-phenol complexes according to thisinvention, are those wherein R is an alkyl or cycloalkyl substituenthaving from 4 to 12 carbon atoms, R is a halogen atom and R is hydrogenor an alkyl substituent containing 1 to 3 carbon atoms. These pretferredcompounds are soluble in and compatible with a wide range of solventsand are very toxic to a wide range of biological materials.

The most preferred ortho-substituted-phenols are the boron complexes of2-chloro-4-isooctyl-G-methylolphenol.

As indicated bereinabove, the biological toxicants can be contacted withthe substratum in any :one of several ways, for example, by mixing,dissolvini spraying and the like. Moreover, if desired, the toxicant canbe associated with an inert carrier and the resultant composition can becontacted with the substratum. 'I his inert carrier can be liquid, solidor gaseous. Thus, the toxioant can be dissolved or dispersed in a liquidinert carrier to form a toxioant-oarrier composition which is thenapplied to a substratum. It will be understood that the toxicants can beprepared and supplied separate from or in combination with a carrier.

While the biological toxicants used in this invention are broadly toxicto all types of biological growth, they are particularly useful incombating micro-organisms and insects such as termites, mosquitos andmoths. T-hese toxicants find particular application in preventingmildew, for example, on leather and plastic goods. These toxic'ants areactive against fungi, bacteria, algae and protozoa.

As will be understood by those skilled in the art, what has beendescribed is the preferred embodiment of the invention. However, manymodifications, changes, and substitutions can be made therein withoutdeparting from the scope and spirit of the following claims.

We claim:

1. A composition of matter comprising (A) a major proportion of -asubstratum and (B) a toxic amount of a compound selected from the \groupconsisting of (1) a compound having the formula:

OCIEH 2 (2) a compound having the formula:

R O OH ]3 M (1110 OH in and mixtures thereof, wherein (a) R and R areeach independently selected from the group consisting of 'halogen,alkyl, cycloal'kyl and aryl substituents; one of said -R and R beinghalogen; the rtotal number of carbon atoms in said R and R substituentscombined being from 4 to 24;

(b) R is selected from the group consisting of hydrogen, alkylsubstituents containing from 1 to 7 carbon atoms, cycloalkylsubstituents containing from 4 to 7 carbon atoms and aryl substituentscontaining from 6 to 10 atoms;

(0) M is selected from the group consisting of alkali metal andammonium.

2. A biologically toxic composition of matter compris- (A) a majorproportion *of a zfinely divided solid and (B) a toxic amount of acompound selected from the group consisting of (1) a compound having theformula:

Rx I

h/ in and mixtures thereof, wherein (a) R and R are each independentlyselected from the group consisting of halogen, alkyl, cycloalkyl "andaryl substituents; one of said Rand R being halogen; the total number ofcarbon atoms in said R and R substituents combined being from 4 to 24;

(b) R is selected from the group consisting of hydrogen, 'alkylsubstituents containing from 1 to 7 carbon 'atoms, cycloalkylsubstituents containing from 4 to 7 carbon atoms and aryl substituentscontaining from 6 to carbon atoms;

(c) M is selected from the group consisting of alkali metal andammonium.

3. A biologically toxic composition of matter comprising (A) a majorproportion of a unitary solid and (B) a toxic amount of a compoundselected from the group consisting of (1) a compound having the formula:

(2) a compound having the formula:

and mixtures thereof, wherein (a) R and R are each independentlyselected from the group consisting of halogen, alkyl, cycloalkyl andaryl substituents; one of said R and R being halogen; the total numberof carbon atoms in said R and R substituents combined being from 4 to24;

('b) R is selected from the group consisting of hydrogen, alkylsubstituents containing from 1 to 7 carbon atoms, cycloalkylsubstituents containing from 4 to 7 carbon atoms and aryl substituentscontaining from 6 to 10 carbon atoms;

(c) M is selected from the group consisting of alkali metal andammonium.

4. A biologically toxic composition of matter comprising (A) a majorproportion of a liquid and (B) a toxic amount of a compound selectedfrom the group consisting of (1) a compound having the formula:

(2) a compound having the formula:

and mixtures thereof, wherein (a) R and R are each independentlyselected from the group consisting of halogen, alkyl, cycloalkyl andaryl substituents; one of said R and R being halogen; the total numberof carbon atoms in said R and R substituents combined being from 4 to24;

(b) R is selected from the group consisting of hydrogen, alkylsubstituents containing from 1 to 7 carbon atoms, cycloalkylsubstituents containing from 4 to 7 carbon atoms and aryl substituentscontaining from 6 to 10 carbon atoms;

(0) M is selected from the group consisting of alkali metal andammonium.

5. A biologically toxic composition of matter comprising (A) a majorproportion of a liquid hydrocarbon and (B) a toxic amount of a compoundselected from the group consisting of (1) .a compound having theformula:

(2) a compound having the formula:

and mixtures thereof, wherein .(a) R and R are each independentlyselected from the group consisting of halogen, alkyl, cycloalkyl andaryl substituents; one of said R and R being halogen; the total numberof carbon atoms in said R and R substituents combined being from 4 to24;

(b) R is selected from the group consisting of hydrogen, alkylsubstituents containing from 1 to 7 carbon atoms, cycloalkylsubstituents containing from 4 to 7 carbon atoms and aryl substituentscontaining from 6 to 10 carbon atoms;

(0) M is selected from the group consisting of alkali metal andammonium.

6. A biologically toxic composition of matter compris- (A) a majorproportion of a surface coating composition and (B) a toxic amount of abiologically toxic compound selected from the group consisting of (1) acompound having the formula:

11 (2) a compound having the formula:

R- OH and mixtures thereof, wherein (a) R and R are each independentlyselected from the group consisting of halogen, alkyl, cycloalkyl andaryl su-bstituents; one of said R and R being halogen; the total numberof carbon atoms in said R and R substituents combined being from 4 to24;

(b) R is selected from the group consisting of hydrogen, alkylsubstituents containing from 1 to 7 carbon atoms, cycloalkylsubstituents containing from 4 to 7 carbon atoms and aryl substituentscontaining from 6 to 10 carbon atoms;

(0) M is selected from the group consisting of alkali metal andammonium.

7. A biologically toxic composition of matter compris- (A) a majorproportion of a cellulosic substance and (B) a toxic amount of abiologically toxic compound selected from the group consisting of (1) acompound having the formula:

(2) a compound having the formula:

n-C -o OH I 0110 la and mixtures thereof, wherein (a) R and R are eachindependently selected from the group consisting of halogen, alkyl,cycloalkyl and aryl substituents; one of said R and R being halogen; thetotal number of carbon atoms in said R and R substituents combined beingfrom 4 to 24;

(b) R is selected from the group consisting of hydrogen, alkylsubstituents containing from 1 to 7 carbon atoms, cycloalkylsubstituents containing from 4 to 7 carbon atoms and aryl substituentscontaining from 6 to 10 carbon atoms;

(0) M is selected from the group consisting of alkali metal andammonium.

(2) a compound having the formula:

R1 R1 l I R o o-n M I 3110 O(|3H R2 R1 (2) a compound having theformula:

R -0\ OH M (3110 OH R2 and mixtures thereof, wherein and mixturesthereof, wherein (a) R and R are each independently selected from thegroup consisting of halogen, 'alkyl, cycloalkyl and aryl suhstituents;one of said Rand R being halogen; the total number of carbon atoms insaid R and R substituents combined being from 4 to 24;

(b) R is selected from the group consisting of hydrogen, alkylsubstituents containing from 1 to 7 carbon atoms, cycloalkylsubstituents containing from 4 to 7 carbon atoms and aryl substituentscontaining from 6 to 10 carbon atoms;

(c) M is selected from the group consisting of alkali metal andammonium.

8. A biologically toxic composition of matter compris- (A) a majorproportion of an inert carrier and (B) a toxic amount of a compoundselected from the group consisting of (1) a compound having the formula:

Ilii If! R o 0 -11 M I pno \O(|3H (a) R and 'R are each independentlyselected from the group consisting of halogen, alkyl, cycloalkyl andaryl substituents; one of said R and R being halogen; the total numberof carbon atoms in said R and R substituents combined being from 4 to24;

(b) R is selected from the group consisting of hydrogen, a'lkylsu-bstituents containing from 1 to 7 carbon atoms, cycloalkylsubstituents containing from 4 to 7 carbon atoms and aryl substituentscontaining from 6 to '10 carbon atoms;

(c) M is selected from the group consisting of alkali metal andammonium.

group consisting of 1) a com-pound having the formula:

Manama/A 4 13 (2) a compound having the formula:

B M 0110 \OH and mixtures thereof, wherein (a) R and "R are eachindependently selected from the group consisting of halogen, alkyl,cycloa-lkyl and aryl s-ubstituents; one of said R and R being halogen;the total number of carbon atoms in said R and R 'substituents combinedbeing from 4 to 24;

( b) R is selected from the group consisting of hydrogen, alkylsubstituents containing from 1 to 7 carbon atoms, cycloalkylsubstituents containing from 4 to 7 carbon atoms and aryl substituentscontaining from *6 to 10 carbon atoms;

(c) M is selected from the group consisting of alkali metal andammonium.

11. A composition of matter comprising (A) a major proportion of asubstratum and ('B) a toxic amount of a compound having the formula:

CH3 CH3 C 3 3 mula:

References Cited by the Examiner UNITED STATES PATENTS 8/ 1936 Honel260619 X 7/1941 Perkins 260-619 6/ 1946 DAlelio 260--619 3/ 1953 Moyleet a1. 260-621 6/195-8' Garner 260-462 4/1959 Lowe 260 462 111/ 1960Boyer t16738.7 6/ 1961 'Leshin 260621 4/1962 Morris et a1 260-621 4/1963 Roberts 260-623 FOREIGN PATENTS 11/ 8 Canada.

5/1953 Germany.

JULIAN S. LEVITT, Primary Examiner. GEORGE A. MENTIS, AssistantExaminer.

9. A METHOD OF COMBATING THE GROWTH OF BIOLOGICAL MATERIAL CHARACTERIZEDBY CONTACTING SAID BIOLOICAL MATERIAL WITH A TOXIC AMOUNT OF A COMPOUNDSELECTED FROM THE GROUP CONSISTING OF (1) A COMPOUND HAVING THE FORMULA: